Di-benzo thiazino pyrroles

ABSTRACT

New heterocyclic compounds of the di-benzothiazino(2,3-b:3&#39;&#39;, 2&#39;&#39;d)-pyrrole series which are suitable as pigment dyes.

Waited States Patent [7 2] Inventors Peter Dimroth Ludwlgshafen; Manfred Gaeng, Roxheim, both of Germany [21] Appl. No. 814,194

[22] Filed Apr. 7, 1969 [45] Patented Nov. 30, 1971 [73] Assignee Badische Anilin- & Soda-Fabrik Aktiengesellschaft Ludwigshafen/Rhine, Germany [32] Priority Apr. 5, 1968 Germany [54] Dl-BENZO THIAZINO PYRROLES [51] lnLCl ..C07d 93/12 [50] Field 0! Search.. 260/243. 243 AN, 243 R [56] References Cited UNITED STATES PATENTS 2,989,529 6/1961 Schuler et al. 260/243 3,299,057 1/1967 Gross et al. 260/243 Primary Examiner-John M. Ford Attorney-Johnston, Root, O'Keefie, Keil. Thompson &

Shunleff ABSTRACT: New helerocyclic compounds of the dibenzothiazino[2,3-b:3',2'd]-pyrrole series which are suitable as pigment dyes.

Dl-BENZO Tl-IIAZINO PYRROLES This invention relates to new heterocyclic compounds of the dibenzothiazino-[2,3b:3',2'd]-pyrrole series which are suitable as pigment dyes.

The new dies have the general formula where X is a single bond or one of the bridging members v Z is an aliphatic, araliphatic or unsaturated cyclic radical free from sulfonic acid groups, Ar is a divalent radical free from sulfonic acid groups which combines with the portion of the molecule to form an aromatic radical, and n is one of the integers l and 2.

Examples of unsaturated cyclic radicals Z are those of benzene, diphenyl, naphthalene and anthraquinone. These radicals may contain, as substituents, halogen atoms such as chlorine or bromine atoms, alkyl radicals such as methyl groups, alkoxy radicals such as methoxy groups, nitro groups, acylamino groups such as benzoylamino groups or acetylamino groups, unsubstituted amide groups and amide groups substituted by phenyl radicals, the latter if desired containing halogen atoms, alkyl radicals or alkoxy radicals.

The aliphatic radicals Z may be derived for example from alkyl radicals having from one to six carbon atoms. They may contain substituents such as cyano groups, unsubstituted amide groups or amide groups substituted by phenyl radicals. Examples of suitable araliphatic radicals are benzoyl radicals. If n in formula I is I, the following are suitable radicals and where R is a hydrogen atom, a halogen atom such as chlorine or bromine atom, or a methoxy group, R is a hydrogen atom, a halogen atom such as a chlorine or bromine atom, or a methoxy or nitro group, R is a hydrogen atom, a halogen atom such as a chlorine or bromine atom, or a methoxy group,

and R is a hydrogen atom, a halogen atom such as a chlorine or bromine atom, or an amide. benzoyl, acetylamino or nitro Suitable radicals Ar which combine with the portion of the molecule to form an aromatic radical are those which together with form a benzene or napthalene ring, the said ring if desired bearing substituents other than sulfonic acid groups. Examples of substituents are halogen atoms such as chlorine or bromine atoms, alkyl groups such as methyl or ethyl groups, alkoxy groups such as methoxy groups, or hydroxyl groups esterified with carboxylic acids, such as propionic acid/The radicals Ar include the following:

Of the dyes of formula I the dyes of formula I a:

y wm r 1 u Ar are of particular industrial interest. in formula l a Ar denotes one of the radicals E one of the radicals Y a CO-NH-- or -NHCO radical, and X is a single bond or one of the radicals The new pigments may for example be prepared by condensing dichloromaleic acid or dichloromaleic anhydride with a compound having the general formula ll: (H N-X (where X, Z and n have the meanings given above) to form a compound of the general formula lll:

III

(where X, Z and n have the meanings given above) and reacting the resultant dichloromaleimide of formula III with an aromatic orthoaminomercapto compound of the general formula IV:

risqz d Dichloromaleimide (a) 01- Cl where Ar has the meanings given above, for example by heating in an organic solvent, advantageously at temperatures of from to 180 C. Organic carboxylic acids such as acetic acid, propionic acid, butyric acid or mixtures containing the same are particularly suitable.

The pigment dyes may be isolated from the reaction mixtures for example by suction filtration, and if necessary they may be purified by heating in organic solvents. The color strength may be increased by bringing the dyes into a fine state of subdivision by conventional methods, for example by dissolution in and reprecipitation from, or swelling in, sulfuric acid, or by grinding in the presence of grinding aids. lf necessary, the dyes may be formulated by dispersion in binders.

The dyes of formula I are suitable for all pigment applications, for example for the production of printing inks and nitrocellulose, acrylate, melamine or urea-formaldehyde based surface coatings, for mass coloring natural and synthetic macromolecular materials, e.g. polyethylene, polyvinyl chloride, polystyrene and rubber, for textile printing and for dope-dyeing.

Coloration of the materials or mixtures of materials is carried out in conventional manner. Yellow to red colorations are obtained, for example brilliant printing, inks and lacquers having high tinctorial strength, or mass colored plastics, which are distinguished by purity of shade, good fastness to overspraying and migration, high thermal stability and good fastness to light. Owing to their high thermal stability the pigments are particularly suitable for coloring synthetic thermoplastics.

The parts and percentages specified in the examples are by weight.

EXAMPLES A. Production of the dichloromaleimides An amino compound of the formula (H N--X),,Z is added to 1,400 parts of glacial acetic acid in an amount (in parts) corresponding to the equivalent weight of the amine. Then l66 parts of dichloromaleic anhydride is added. The whole is heated for 1 hour at 60 C. and for 4 hours at 1 10 C., and the product is filtered cold, washed with a little methanol and dried. The dichloromaleimides listed in table I under a are obtained in yields of 30 to 95 percent.

B. Production of the pigments Table] Dichloromaleimide (v. table I) is added to 5,000 parts of glacial acetic acid in an amount (in parts) corresponding to its molecular weight. Then 280 parts of o-aminomercaptobenzene is dripped in. The whole is stirred for l hour at 40 C., for another hour at 80 C., and for 6 hours at 1 10 C. The product is allowed to cool, washed with glacial acetic acid and methanol and dried. Pigments are obtained in the yields given in table I under b.

Table ll Dichloromaleimide as specified in the table is added to 600 parts of glacial acetic acid in an amount (in parts) corresponding to one tenth of its molecular weight. Then one of the aminomercapto compounds specified is added in an amount (in parts) corresponding to one quarter of its molecular weight. The mixture is stirred for l hour at 60 C., for another hour at C., and for 6 hours at 1 10 C. The product is filtered cold, washed with glacial acetic acid and methanol and dried. The pigments are obtained in the yields given in table ll.

TABLE 1 (-x z \"illd Number (in a and b) [lurcontl 1 -T--@ 15 2 -CONII--Cl 110 211 4 1 A. C()N|h H5 200 CONH- CONHOOH:

s OOH; 35 200 m Cl 111 200 I 11 so NH-C 0- 13 31 use 1s NO= 19s 111m. ms

5 Ruddlshm'nngu.

XI) H0.

75 ()mngu.

75 Reddish orange.

Orange.

80 Reddlsh orange.

80 Orange.

65 Reddish orange.

00 Orange.

00 Yollowlsh orange.

Number (in u and h) Q 4; CONH-Q-NH 0 OCH3 7'.) Reddlsh orange.

TABLE II Yield Shmlo Aminomercapto Number compound used 80 Brown.

70 Orange brown.

60 Brown.

60 Orange brown.

70 Red.

HaC 0 75 Roddlsh orange.

70 Red.

65 Orange red.

65 Red.

Aminomercapto Number compound used X ,.-Z Ylold Slmdu 14 t v till D0.

CzHsOCO SII OONll-- -Nl l 15 t 55 llrown.

N O z- -NH 16 e 60 Orange.

17 80 Rod.

(11- SH 0 0 NH- l8 78 Orange.

Cl 811 Cl -Nllz (lo-NH 19 SH Red.

NH--C 0 IIIH- O C. Use of the pigments 55 Example 3 EXAMPLE I One part of the pigment designated No. l in table I is triturated on a three-roll mill with l0 parts of linseed oil varnish. The printing ink thus obtained gives orange prints having excellent brilliance and lightfastness when used in book printing. Similar results are obtained by using the other pigments listed in tables I and ll.

Example 2 Ninety-five parts of a baking finish-comprising 67 parts of coconut oil resin, 17 parts of urea-formaldehyde resin and l6 parts of ethylene glycol is triturated in suitable equipment with 8 parts of the pigment designated No. l in table I. The resultant reddish orange lacquer may be applied to metal sheet, cardboard or aluminum foiland gives reddish orange colorationshaving excellent fastness to overspraying and light after baking. Similar results are obtained by using the other pigments listed in tables I and II.

A mixture of 70 parts of polyvinyl chloride, 30 parts of diisooctyl phthalate and one part of titanium dioxide is colored in conventional manner on rollers heated to I60 C.

60 with 0.5 part of the pigment designated No. l in table I. A reddish orange PVC composition is obtained which may be used for example for the manufacture of sheet or profiles. The coloration is distinguished by high brilliance and good plasticizer and light fastness. Similar results are obtained by 65 using the other pigments listed in tables I and ll.

We claim: 1. A dye having the formula wherein Ar is a divalent radical combining with the C=C- portion of the molecule to form an aromatic ring selected from the group consisting of benzene, naphthylene and benzene substituted by chlorine. bromine, methyl. ethyl. methoxy, nitro or OCOC,H,, and n is one of the integers l 5 and 2 such that:

A. when is the integer l. the monovalent radical X-Z is selected from the group consisting of lln N/ Nll- Nil ui,

No, 6 NH mun. m 5

NH Nil no on, UN,

I .4 um e0--Nn--,

l N (l': 0 (l.

l t (.()--Nll m It w undin which R is divalent phenyl, biphenyl or naphthyl and in which phenyl groups may be substituted by chlorine or methoxy.

2. A compound as claimed in claim 1 of the formula wherein Ar denotes a radical selected from the group consist- 7 ing of 5.

E denotes a radical selected from the group consisting of Y denotes a radical selected from the group consisting of CO-NH- and -NH-CO, and

X denotes a single bond or a radical selected from the group consisting of 3. The dye having the formula CO-Nll UNITED STA'X'ES PA'lEN'l Oi FICE CER'FLFICATE 0F CORRECTKON Patent No. "9' 62"? O80 Dated November 50 lfj'fl Iuvuutor(s) ,u(,i' Dimruth 11ml I-iuAlflCL i Gaenp;

It is certified that error appears in the above-identificd p:..i:ent

and that said Letters Patent are hereby corrected as shown helm:

mmx

I Column 3, line t}, (HaNmXhWH shouic' read (H NX) -Z II F fl n column 1), llncs 5/ to clalm 1:

should read Column 15, line 72, to column 16, line 15, claim 2, 2.A compound as claimed in claim 1 of the formula denotes a radical selected from the group consistwherein Ar ing of should read 2. A compound as claimed in claim -1 of the formula 8 B a U i e j" W lF-Y N N N [1/ 1 S S In wherein Ar denotes a radical selected from the group consisting of Signed and sealed this 9th day of May 1972.

(smL) Attcst:

E JL'JARD P I.FLi:ITCI-IHIR,JR. ROBERT GOT'I'SCHALK Attestlng: Officer Commissioner of Patents 

2. A compound as claimed in claim 1 of the formula
 3. The dye having the formula 